Process for dyeing polyhydroxylated materials and preparations therefor



United Stats 3,631,252 Patented Apr. 24, 1962 PROCESS FOR DYEINGPOLYHYDRGXYLATED MATERIALS AND PREPARATIONS THEREFOR Max Staeuble andPeter Stahel, Basel, Switzerland, as-

signors to Ciba Company, lne, Fair Lawn, NJ. No Drawing. Filed Apr. 7,1958, Ser. No. 726,639 Claims priority, application Germany Apr. 18,1957 8 Claims. (Cl. 8-34) This invention provides a process for dyeingpolyhydroxylated materials, such as textile materials of polyvinylalcohol or especially of cellulose, with compounds capable of beingvatted, which contain at least one hydrophilic group and at least onegroup capable of being chemically fixed, wherein at least one stage ofthe process carried out in the presence of a reducing agent.

As compounds capable of being vatted there may be mentioned principallythose of the anthraquinone series. As other vattable compounds there maybe mentioned those of the perinone-series or peri-dicarboxylic acidirnide series. The vattable compounds must contain at least onehydrophilic group, for example, one or more hydroxyl, amino,hydroxyalkylamino, quaternary ammonium, sulfonamide or methyl-sulfouegroups, and especially carboxylic acid or sulfonic acid groups. Thecompounds used in this process also contain at least one group capableof being chemically fixed, that is to say, a 7

group capable of reacting with the hydroxyl groups of thepolyhydroxylated material to form a stable chemical bond. As such groupsthere may be mentioned more especially those which contain at least onemobile halogen atom.

Of special interest are dyestuffs which contain a group of the formula1,. Z i t in which n is a whole number not greater than 5, Z representsa chlorine atom or a hydroxyl, alkoxy, or amino group which may besubstituted by an alkyl, hydroxyalkyl, for example, hydroxyethyl, groupor by a colorless or colored aryl residue, especially one containing agroup imparting solubility in water.

As an example of a colorless aryl radical there may be mentioned thebenzene radical, and as an example of a colored aryl radical there maybe mentioned an arylamino-anthraquinone radical.

The dyestulis used in the process of the invention are made by methodsin themselves known, for example, by reacting a vattable compound, whichcontains a lhydrophilic group and a reactive amino group, with acompound which contains at least two mobile halogen atoms, and, ifdesired, replacing a mobile halogen atom in the compound so obtained byanother substituent, the starting materials being so selected that atleast one component contains a hydrophilic group, and the conditionsbeing such that the final dyestufistill contains a mobile halogen atom.I

The dyestufis so obtained can be used for impregnating on a foulard ordyeing in a dyebath cellulosic materials or synthetic fibres, forexamples, regenerated cellulose or viscose, or natural materials such aslinen or above all cotton. For this purpose there are advantageouslyused aqueous solutions of the dyestuifs. Cotton may also be dyed withthe aforesaid dyestulfs by the known pad roll method, in which thegoods, after being foularded are wound on a roller and dyed thereon foralong time while slowly rotating the goods at the desired temperature.

The dyeing can usually be carried out with advantage at temperaturesbelow those customary in dyeing cotton, for example, below C., forexample, at about 50 C. In order to exhaust the dyebath it is ofadvantage to add to the dyebath, if desired in portions, a more or lessneutral and preferably inorganic salt, such as an alkali chloride orsulfate, simultaneously with the dyestuif or during the dyeing process.During the dyeing process the dyestuif containing the labile groupreacts with the cellulosic material to be dyed, on Which the dyestuif isfixed probably by a chemical bond. In order to assist this fixingprocess during or at the beginning of the dyeing process the dyebath maybe rendered distinctly alkaline by the addition of an alkali, forexample, by the addition of sodium carbonate, potassium carbonate or asolution of caustic alkali. Furthermore, the pH value of an initiallyweakly acid to neutral or weakly alkaline dyebath may be graduallyincreased during the entire dyeing process or, after applying thedyestuit to the material to be dyed, the material may be treated, ifdesired after being dried, in a fresh alkaline bath in order to fix the\dyestuff.

As reducing agents there may be used strong reducing agents, such assodium hydrosulfite or weaker reducing agents, such as sodium sulfide,sodium hydrosulfide or glucose. The proportion of the reducing agent mayvary within wide limits. In most cases it is sufficient to use aconsiderably smaller quantity of reducing agent than is usuallynecessary for dyeing with vat dyestuffs or sulfur dyestulfs.

The reducing agent may be added at the outset, halfway through ortowards the end of the dyeing process.

Instead of preparing the dyebath by taking up the vattable compound,reducing agent, and, if desired, more or less neutral inorganic salt inwater simultaneously or separately in succession, the dyestuii and thesalts may be worked up into a paste-like preparation or advantageously adry preparation. As some of the vattable compounds used in the processare somewhat sensitive towards alkalies owing to their content of labilesubstituents, it is of advantage to incorporate in the preparations assmall a quantity as possible of salts having an alkaline reaction inwater. In the case of certain of the vattable compounds defined abovethere may be incorporated with the preparations, instead of or inaddition to the salt, a non-electrolyte such as urea.

By the process of this invention there are produced on polyhydroxylatedmaterials, especially cellulosic textile materials, dyeings or printshaving excellent properties of wet fastness and a very good fastness tolight.

As compared with the traditional vat dyeing process, the process of thepresent invention has the advantage of being simpler to operate, becausethe vatting that precedes dyeing is dispensed with and the process islargely independent of temperature.

The following examples illustrate the invention, the parts andpercentages being by weight:

3 Example 1 2 parts of the dyestuft' of the probable formula S0311 aredissolved in 2000 parts of water. 20 parts of trisodium phosphate and250 parts of sodium chloride solution of 20% strength are added. 100parts of well wetted cotton satin are entered into the dyebath at 20-25C. In the course of 20 minutes the temperature is raised to 5060 C. andthen a further 250 parts of sodium chloride solution of 20% strength areadded. After a dyeing period of 30 minutes, 5 parts of sodiumhydrosulfite are added and dyeing is continued for a further 45 minutesat 50-60 C. The red-violet dyeing is then reoxidized in the air or bythoroughly rinsing it in a dilute aqueous solution of an oxidizingagent, for example, hydrogen peroxide or sodium perborate. The materialis then soaped for minutes at the boil with a non-ionic detergent,rinsed in cold water, and dried. There is obtained a blue-red dyeing ofgood fastness to washing.

Instead of trisodium phosphate, there may be used sodium carbonate orcaustic soda solution.

There may also be used as reducing agent glucose, sodium hydrosulfide orsodium sulfide.

The dyestutf used in this example can be prepared in the mannerdescribed in patent application Serial No. 720,528, filed March 11, 1958(now US. Patent No. 2,914,531), by condensing the compound of theformula /CO C s o H 00 with 2:4 dichloro 6 phenylamino 1:3:5 triazine4'-su1fonic acid in aqueous solution with the addition of sodiumcarbonate.

Example 2 2 parts of the dyestufi' of the formula Q C 0 803B:

4 are used for dyeing in a manner analogous to that of the dyestufi ofExample 1. There is obtained a grey dye- Example 3 2 parts of thedyestufi of the formula (I) NH,

SOaH

(In H O NH-C/ \N SOzH N=o| G are used for dyeing in a manner analogousto the dyestufi described in Example 1, with the exception that thedyeing temperature is raised in the course of 30 minutes from 20-25" C.to 8085 C. and that the reducing agent, consisting of 3.5 parts ofcalcined sodium sulfide, is added to the dyebath at the outset with thealkali. There is obtained a violet dyeing.

The dyestuff used in this example can be prepared in the mannerdescribed in patent application Serial No. 682,599, filed September 9,1957, by Jakob Brassel et al. by condensing1:4-diaminoanthraquinone-2-sulfonic acid with 2:4 dichloro-6-phenylamino123:5 triazine-3-triazine-3'-sulfonic acid in aqueous solution with theaddition of sodium carbonate.

Example 4 2 parts' of the dyestufi of the formula (M Ho's CHN 0 are usedfor dyeing in the manner described in Example 3. There is obtained asalmon colored dyeing.

The dyestufi used in this example can be prepared in are used for dyeingin a manner analogous to that of the the manner described in patentapplication Serial No. dyestufi in Example 1. There is obtained ared-orange 682,599, filed September 9, 1957, by Jakob Brassel et a1.dyeing of good fastness to washing and light. by condensing1:S-diaminoanthraquinone-2-sulfonic acid The dyeings obtained asdescribed in Examples 5 and W1th 2:4 d1ch10ro-6-ph ny a a p9 $111- 5 6are considerably deeper in tint and purer in shade than 9 acld 111aqueous solutlml Wlth the addition of the corresponding dyeings producedwithout the use of a (hum Carbmlaie. rgducing agent Example 5 Thedyestufi used in Example 5 can be made in the 2 parts of the dyestutf:of the formula manner described in patent applicationSerial No.720,528,

are used for dyeing in manner analogous to that of the 20 filed March11, 1958, by condensing the product of the dyestufi of Example 1. Thereis obtained a strong red formula with1--phenylamino-4-amino-thioxanthone sulfonic acid in aqueous solutionwith the addition :of :sodium cardyeing of very good fastness to washingand chlorine. b

The above dyestufi' can be made in the manner de- Example 7 scribed inpatent application Serial No. 720,528, filed 35 2 parts of the dyestufiof the formula 0 0 II 'II 0 O 01 HO 8 son '01 N N a R I IH0aSOHN-C\N/CHN \N -NHO\C%CNH SOaH March 1-1, 1958, by reacting thecondensation product of are used for dyeing in a manner analogous tothat of the the formula dyestuflf of Example 1. There is obtained abrown dyeing H g p C l 0 I 01 01 with ethanolamine in aqueous solution.

of 'very .good fastness to Washing.

Example 6 The dyestufl used in this example can be prepared in Parts ofthe dyesmfipof the formula 60 the manner described 1n patent applicationSerial No.

1| i N 11038 /C C\ SOaH H 014 K -HN N\ /NNfll(i ?Cl N C/ C o I! H G 0 oy l NH NH S a II t -Q SOaH H033 7 8 720,528, filed March 11, 1958, bycondensing the product Weight increase of 75 and dried. The dyeing isthen of formula fixed by treating the fabric for 45 minutes on a jiggerin a solution, at 80 C., which contains, per liter, 10 O C grams ofsodium hydroxide, 300 grams of sodium chlo- Hois ride and 30 grams ofsodium hydrosulfite. The fabric is then thoroughly rinsed in water,soaped for hour at 0 o the boil in a solution of 0.3% strength of anon-ionic de- HIN N/ \N NE: te -gent, rinsed and dried. There isobtained a red dyeing of good fastness to Washing.

with 2:4-dichloro 6 phenylamino-l 3 :5 triazine-4'-sul- Instead of usingthe above brs-(dlchlorotnazlne) comfonic acid in the presence of sodiumcarbonate.

Example 8 pound, the same good result can be obtained with the cor- 3parts of the dyestuft' of the probable formula respondingbis-(monochlorotriazine) compound.

0 0 01 1| ll 01 (|3 N H03? o o\ S0311 N (|3 k N o-HNON N -NH-C N =i NHNH 2 (I; g i

are dissolved in 100 parts of water. A cotton fabric is Example 11impregnated with the cooled solution in such manner that 2 pal-ts f mdye t fl f the f l its weight increases by 75%, and the fabric is thendried. O

The fabric is then impregnated with a solution, at l 40 C., whichcontains, per liter, 10 grams of sodium hy- COOH droxide, 300 grams ofsodium chloride and 30 grams of sodium hydrosulfite, the fabric issqueezed to a Weight increase of 75 and the dyeing is steamed for 60seconds at 100-101 C., then thoroughly rinsed in cold wa- \C. NH C -CQOHter, treated in a sodium bicarbonate solution of 0.5% Q 1 strength,rinsed, soaped for 20 minutes at the boil in a solution of 0.3% strengthof a non-ionic detergent, rinsed C and dried. There is obtained a reddyeing which is fixed fast to boiling. are used for dyeing in the mannerdescribed in Example There y also be used as reducmg agent glucose or 3.There is obtained a reddish blue dyeing of very good sodium sulfide.fastness to washing and light.

Instead Of using the above bis-(monochlorotriazine) Th dyestufl used inthis example can be made as decompound the same good result can beobtained by using scribed in patent application Serial No. 682,599,filed the Corresponding bis'(dichlofotriazine) ,compollnd- September 9,1957, by Jakob Brassel et al. by the reac- Example 9 tion of1:4-diaminoanthraquinoue-Z-carboxylic acid with the monocondensationproduct of cyanuric chloride and 2 parts of the dyestufl obtained asdescribed in Exam- 4 aminobenzoic acid.

ple 8 are mixed with 20 parts of urea and dissolved in What is claimedis:

24 parts of Water, and the mixture is stirred in 40 parts 1. A processfor dyeing and printing cellulose textile of a sodium alglnatethickening of 5% strength. There materials with a vat dyestufi of theformula are then added 9 parts of a sodium carbonate solution of N 10%strength, 2 parts of sodium hydrosulfite and 1 part of a 10 N-solutionof caustic soda. i-

A cotton fabric is printed with the resulting printing N color, thendried, steamed for 7 minutes at 100-101 C.,

thoroughly rinsed in water, and soaped for 20 minutes at the boil in asolution of 0.3% strength of a non-ionic de- C1 urgent There is obtaineda bright red print which is in which D represents the radlcal of avattable amine bound to the triazine nucleus through its nirogen atomfixed fast to boning and containing at least one acid group impartingsolu- Example 10 brlrty in water, Z represents a member selected from2.5 parts of the dyestuff of the probable formula the group consistingof a chlorine atom, an amino group,

0 0 01 II II 01 (IFN 30,3 /0 o\ SOIH N 5 N\ C-HN N N NH-C N C=N N=O l CC I Cl I I; 01

are dissolved in 100 parts of water. A cotton fabric is a substitutedamino group, a hydroxy group and a subimpregnated with the resultingsolution, squeezed to a stituted hydroxy group, and n is a whole numberof at 3,031,252 9 to most 5, which process is carried out in thepresence of in the presence of sodium sulfide as reducing agent, triareducing agent selected from the group consisting of an sodium phosphateas alkali and sodium chloride. alkali hydrosulfite, an alkali sulfide,an alkali hydrosul 5. A process for dyeing and printing cellulosetextile fide and glucose, and an alkali selected from the groupmaterials with the dyestufi of the formula in the presence of sodiumhydrosulfite as reducing agent, trisodium phosphate as alkali and sodiumchloride.

6. A process for dyeing and printing cellulose textile materials withthe dyestuff of the formula consisting of an alkali hydroxide, an alkalicarbonate and an alkali phosphate.

2. A process for dyeing and printing cellulose textile 0 0 01 [I ll 01Hogs o 0 $0311 I I N C-HN N N--HNC N =N \C C/ NH: II II NH:

0 0 materials with the dyestutf of the formula in the presence of sodiumhydrosulfite as reducing agent,

sodium hydroxide as alkali and sodium chloride.

7. In a process for dyeing and printing cellulose textile materials witha dyestuli of the formula '0 n1 2n1 N 01 i D-N-(|) (IIJZ S0 H fi I a N\/N NH-C c--NH- 40 1n WhlCh D represents the radical of a vat dyestuffwhich contains 1 to 4 hydrophilic groups, m represents a Whole number upto 2, Z represents a member selected from O the group consisting of achlorine atom, an amino group,

a substituted amino group, a hydroxy group and a substituted hydroxygroup, and n is a whole number of at most 5, in the presence of analkali, the improvement which consists of carrying out the process inthe presence in the presence of sodium hydrosulfite as reducing agent,of a reducing agent selected from the group consisting trisodiumphosphate as alkali and sodium chloride. of an alkali hydrosulfite, analkali sulfide, an alkali hy- 3. A process for dyeing and printingcellulose textile drosulfide and glucose. materials with the dyestufi ofthe formula 8. A process for dyeing and printing cellulose textile 0 NH,materials with a vat dyestutf which contains 2 to 4 acid I groupsimparting solubility in water and corresponds to son: the formula ?1 g%NC C n-1H2n-l NH-C /N so H M -f 1H NE N N in the presence of sodiumsulfide as reducing agent, tn- 3 sodium phosphate as alkali and sodiumchloride. 01 m 4. A process for dyeing and printing cellulose textilematerials with the dyestufi of the formula 5 0 z in which K is theradical of a peri-tetra-carboxylic acid diimide containing at least twoof the aforesaid groups 8 3 imparting solubility in water, In representsa whole num- 1 her up to 2, Z is a member selected from the groupconsisting of Cl, NH substituted amino, hydroxy and H substitutedhydroxy, and n is a whole number of at most 5, which process is carriedout in the presence of (a) a reducing agent selected from the groupconsisting of I an alkali hydrosulfite, an alkali sulfide and glucose,(b) NH an alkali selected from the group consisting of an alkali 1 1hydroxide, an alkali carbonate and an alkali phosphate, 1,832,425 and(c) a water-soluble inorganic salt. 1,886,480

References Ciied in the file of this patent UNITED STATES PATENTS 52914531 1,523,308 Steinbuch et al Jan. 13, 1925 12 Remlein Nov. 17, 1931Haller et a1. Nov. 8, 1932 Kunz et a1. Nov. 22, 1932 Brassel et a1. Dec.11, 1956 Staeuble et a1 Nov. 24, 1959

1. A PROCESS FOR DYEING AND PRINTING CELLULOSE TEXTILE MATERIALS WITH AVAT DYESTUFF OF THE FORMULA